Pt/NbPWO双功能催化剂的制备及氢解碱木质素制备芳香单体

木质素是一种天然芳香族聚合物,约占木质纤维素的30%,是唯一通过裂解C―O醚键和C―C键生产芳香族化学品或液体燃料的可再生芳香族资源。迄今为止,对木质素氢解制备有价值化合物的研究主要集中在相对不稳定的C―O键的裂解上,这限制了木质素氢解的效率。采用水热法和湿浸渍法制备了多功能Pt/NbPWO催化剂。通过破坏碱木质素中的C―O键和C―C键,可以得到产率为18.02%的芳香族单体。该反应不仅可以断裂木质素聚合物中醚键,同时也可以断裂部分关键的C―C键。其氢解机理可能是丰富的Brønsted酸和Lewis酸位点参与了C―C的活化。此外,重点分析载体和Pt物种在Pt/NbPWO催化剂中的协同作用。     

Analytical Methods for Determination of Phytic Acid and Other Inositol Phosphates: A Review

From the early precipitation-based techniques, introduced more than a century ago, to the latest development of enzymatic bio- and nano-sensor applications, the analysis of phytic acid and/or other inositol phosphates has never been a straightforward analytical task. Due to the biomedical importance, such as antinutritional, antioxidant and anticancer effects, several types of methodologies were investigated over the years to develop a reliable determination of these intriguing analytes in many types of biological samples; from various foodstuffs to living cell organisms. The main aim of the present work was to critically overview the development of the most relevant analytical principles, separation and detection methods that have been applied in order to overcome the difficulties with specific chemical properties of inositol phosphates, their interferences, absence of characteristic signal (e.g., absorbance), and strong binding interactions with (multivalent) metals and other biological molecules present in the sample matrix. A systematical and chronological review of the applied methodology and the detection system is given, ranging from the very beginnings of the classical gravimetric and titrimetric analysis, through the potentiometric titrations, chromatographic and electrophoretic separation techniques, to the use of spectroscopic methods and of the recently reported fluorescence and voltammetric bio- and nano-sensors.     

Sensing of Phosphates by Using Luminescent EuIII and TbIII Complexes: Application to the Microalgal Cell Chlorella vulgaris

Phenanthroline‐based chiral ligands L¹ and L² as well as the corresponding Eu^III and Tb^III complexes were synthesized and characterized. The coordination compounds show red and green emission, which was explored for the sensing of a series of anions such as F^?, Cl^?, Br^?, I^?, NO₃^?, NO₂^?, HPO₄^2?, HSO₄^?, CH₃COO^?, and HCO₃^?. Among the anions, HPO₄^2? exhibited a strong response in the emission property of both europium(III) and terbium(III) complexes. The complexes showed interactions with the nucleoside phosphates adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP). Owing to this recognition, these complexes have been applied as staining agents in the microalgal cell Chlorella vulgaris. The stained microalgal cells were monitored through fluorescence microscopy and scanning electron microscopy. Initially, the complexes bind to the outer cell wall and then enter the cell wall through holes in which they probably bind to phospholipids. This leads to a quenching of the luminescence properties.     

Synthesis of Two‐Dimensional Transition‐Metal Phosphates with Highly Ordered Mesoporous Structures for Lithium‐Ion Battery Applications

Materials with ordered mesoporous structures have shown great potential in a wide range of applications. In particular, the combination of mesoporosity, low dimensionality, and well‐defined morphology in nanostructures may exhibit even more attractive features. However, the synthesis of such structures is still challenging in polar solvents. Herein, we report the preparation of ultrathin two‐dimensional (2D) nanoflakes of transition‐metal phosphates, including FePO₄, Mn₃(PO₄)₂, and Co₃(PO₄)₂, with highly ordered mesoporous structures in a nonpolar solvent. The as‐obtained nanoflakes with thicknesses of about 3.7 nm are constructed from a single layer of parallel‐packed pore channels. These uniquely ordered mesoporous 2D nanostructures may originate from the 2D assembly of cylindrical micelles formed by the amphiphilic precursors in the nonpolar solvent. The 2D mesoporous FePO₄ nanoflakes were used as the cathode for a lithium‐ion battery, which exhibits excellent stability and high rate capabilities.     

Rb2[U(NH2)6], a Rubidium Hexaamidouranate(IV) obtained from the Reaction of UI3 with RbNH2 in Anhydrous Ammonia

The pyrophoric compound Rb₂[U(NH₂)₆] was obtained as a grey to black powder from the reaction of more than three equivalents of RbNH₂ with UI₃ in anhydrous liquid ammonia. During the process, U^III is oxidized to U^IV and ammonia is reduced under evolution of H₂. Rb₂[U(NH₂)₆] crystallizes in the cubic crystal system, space group Fm3 m, with the lattice parameter a = 9.7870(12) Å, V = 937.4(2) ų, Z = 4 at T = 293 K. It is isotypic to K₂PtCl₆. The compound contains the unprecedented hexaamidouranate(IV) anion [U(NH₂)₆]^2–.     

碱木素的近红外光谱吸收机理的研究

通过碱木素模型物对醌、邻醌和香兰素的溶液在800～900 nm的近红外光谱波段内的吸收谱图的对比发现,对醌和邻醌在此波段产生较强的吸收,而香兰素基本上没有吸收,证明了碱木素的醌型结构在800～900 nm波段内产生特征吸收。对银杏和夹竹桃磨木木素碱处理前后的溶液在800～900 nm波段内的吸光度的差别分析,发现夹竹桃的磨木木素的吸光度的相对变化更大,这是由于夹竹桃磨木木素经碱处理后产生了更多的醌型结构。这也是在硫酸盐法蒸煮过程中在800～900 nm波段内阔叶材的蒸煮液吸光度大于针叶材的蒸煮液吸光度的主要原因。     

Intensification of delignification of Tectona grandis saw dust as sustainable biomass using acoustic cavitational devices

Delignification of sawdust was studied using ultrasound assisted alkali peroxide approach using longitudinal horn for the first time and the efficacy compared with more commonly used configurations of ultrasonic reactors. Comparison with the conventional approach based on stirring has also been presented to establish the process intensification benefits. Effect of different operating parameters such as sodium carbonate concentration (0.1, 0.15, 0.2, 0.25 M), hydrogen peroxide concentration (0.2, 0.4, 0.6, 0.8, 1 M) and biomass loading (2, 4, 6, 8, 10 wt%), on the efficacy of lignin extraction has been investigated for different ultrasonic reactors. The optimum conditions for probe type ultrasonic horn were established as 150 W, 50% duty cycle and 80% amplitude with optimum process conditions as Na₂CO₃ concentration as 0.2 M, H₂O₂ concentration as 1 M, biomass loading of 10 wt% and operating time of 70 min. Longitudinal horn resulted in best efficacy (both in terms of yield and energy requirements) followed by ultrasonic horn and ultrasonic bath whereas the conventional approach was least effective. The obtained lignin was also analyzed using different characterization techniques. The presence of peaks at wavelength range of 875–817, 1123–1110, and at 1599 cm⁻¹ for the extracted sample confirmed the presence of lignin. Increase in the crystallinity index of the processed sample (maximum for longitudinal horn) also confirmed the lignin removal as lignin is amorphous in nature. Overall it has been concluded that ultrasound can be effectively used for delignification with longitudinal horn as best configuration.     

铟（Ⅲ）的碱金属卤化物与冠醚配合物的合成及表征

在萃取研究过程中,合成了10种由四溴(或碘)合铟(Ⅲ)配阴离子与苯并-15-冠-5或二苯并-18-冠-6合钾(或钠)配阳离子相结合所形成的新型固体配合物。经元素分析、红外光谱及差热-热重等方法对配合物进行了表征。通过与相应的冠醚碱金属苦味酸盐配合物结构性质的对比,较合理地解释了这两类萃取体系之间存在的某些差别。     

多级孔HZSM-5分子筛催化剂的制备及低碳烃芳构化应用

采用0.2 mol/L的NaOH溶液对HZSM-5分子筛进行了不同时间的碱改性处理, 并对分子筛的结构和酸性进行表征, 考察了碱改性对HZSM-5催化剂的低碳烃芳构化活性的影响. 结果表明, HZSM-5分子筛经碱改性后会产生少量介孔, 且随改性时间延长, 介孔数量增加, 平均孔径增大, 总酸量降低, B酸/L酸比值降低. 120 min碱改性HZSM-5催化剂的活性、 稳定性以及目标产物苯、 甲苯、 乙苯和二甲苯(统称BTEX)的选择性最高.     

微波消解-电感耦合等离子体发射光谱(ICP-OES)法测生物质中的碱金属和碱土金属

为研究并解决测试生物质样品中碱金属和碱土金属含量的干扰,采用微波消解-电感耦合等离子体发射光谱(ICP-OES)法对生物质中的碱金属和碱土金属钾、钙、钠、镁元素进行测定,考察了样品消解后不同的酸体系,共存元素干扰对钾、钠、钙、镁含量测定的干扰研究。经过研究表明,接近分析标准曲线酸浓度的样品干扰小,铅、铟、钛、锰元素对钠元素测定造成干扰,砷、铜、镉对钙元素测定干扰,铝对钾元素测定有干扰,镁测定不受共存元素干扰影响,运用干扰系数法可以减少共存元素对测定元素的误差。各待测元素标准曲线相关系数大于0.9996,检出限为0.0014~0.023 mg/L,玉米芯各元素的相对标准偏差为0.98%~1.9%,加标回收率为80.2%~106%;西瓜皮的各元素相对标准偏差为0.91%~2.3%,加标回收率为85.3%~106%。方法用于测定国家标准物质GBW07603,各元素结果均在标准值参考范围内。方法用于测定生物质中碱金属和碱土金属的结果,用t检验法与离子色谱测定值进行比对,结果无显著性差异。